CN101665619B - Egg-shell powder filled poly-lactic acid composite material and preparation method thereof - Google Patents
Egg-shell powder filled poly-lactic acid composite material and preparation method thereofDownload PDFInfo
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Abstract
Translated fromChineseDescription
Translated fromChinese技术领域technical field
本发明涉及一种聚乳酸复合材料及其制备方法，尤其是指一种蛋壳粉填充可生物降解聚乳酸的复合材料及其制备方法。The invention relates to a polylactic acid composite material and a preparation method thereof, in particular to a composite material filled with eggshell powder and biodegradable polylactic acid and a preparation method thereof.
背景技术Background technique
我国是世界上养禽最多的国家，其产蛋量已连续20年居世界之首位。我国虽然有丰富的蛋壳资源，但加工利用蛋壳的厂家却微乎其微，蛋壳的开发研究也很薄弱，大量的鸡蛋壳被废弃。按蛋壳占整蛋质量的12％计算，我国每年会产出400多万吨蛋壳。这些未被利用的蛋壳成批地抛入垃圾堆，不仅对环境造成污染，也是资源的浪费。若将蛋壳收集起来，进行综合利用，既可增加经济效益，又可避免对生态环境的污染。在蛋壳开发利用方面，发达国家在技术上领先一步，美国科学家将蛋壳和壳膜完全分离后把蛋壳用于营养制造业、制药业和化工业等方面，而日本则利用蛋壳制作的蛋壳补钙，吸收率大于普通钙源。中国专利CN1077118A用禽蛋壳经电解、真空高温抽取生物活性钙素，用作食品强化剂；中国专利CN111514A用壳内膜提取蛋膜素，应用于化妆品之中。目前尚未发现蛋壳作为塑料填料的研究。my country is the country that raises the most poultry in the world, and its egg production has ranked first in the world for 20 consecutive years. Although my country is rich in eggshell resources, there are very few manufacturers that process and utilize eggshells, and the development and research of eggshells is also very weak, and a large number of eggshells are discarded. According to the calculation that eggshells account for 12% of the whole egg mass, my country will produce more than 4 million tons of eggshells every year. These unused eggshells are thrown into the garbage dump in batches, which not only pollutes the environment, but also wastes resources. If the eggshells are collected and used comprehensively, economic benefits can be increased and pollution to the ecological environment can be avoided. In the development and utilization of eggshells, developed countries are one step ahead in technology. American scientists completely separate eggshells and shell membranes and use eggshells in nutrition, pharmaceutical and chemical industries, while Japan uses eggshells to make eggs. The eggshell calcium supplement, the absorption rate is greater than that of ordinary calcium sources. Chinese patent CN1077118A uses poultry egg shells to extract bioactive calcium through electrolysis and vacuum high temperature, which is used as a food fortifier; No research has been found on eggshells as plastic fillers.
另外，随着全球经济的不断发展，工农业对石油资源消耗的不断增加，使石油资源面临枯竭，另一方面各种依赖石油的不可降解塑料用量却在不断增长，造成严重的白色污染，给世界可持续发展带来了巨大的挑战。生物可降解材料聚乳酸以其具备可降解的优异特性大有取代传统塑料的趋势。聚乳酸是一种以可再生植物资源为原料经过化学合成制备的生物降解高分子材料，摆脱了对传统资源的依赖，其生产制造过程造成的环境污染小，且具有良好的生物降解性，降解产生的二氧化碳和水可以返回自然界，重新参加植物的光合作用，从而维持自然界的碳循环平衡，满足可持续发展的要求，大力开发环境友好型生物降解高分子材料已经引起了世界各国广泛的关注，中国也不例外。对此，国家不断加大对这方面的科研投资力度，并且已列入国家支撑项目等重大研究计划。In addition, with the continuous development of the global economy, the consumption of petroleum resources by industry and agriculture continues to increase, causing the petroleum resources to be exhausted. Sustainable development in the world poses enormous challenges. The biodegradable material polylactic acid has a tendency to replace traditional plastics due to its excellent characteristics of degradability. Polylactic acid is a biodegradable polymer material prepared by chemical synthesis using renewable plant resources as raw materials. It gets rid of the dependence on traditional resources. The carbon dioxide and water produced can be returned to nature and participate in the photosynthesis of plants, thereby maintaining the carbon cycle balance in nature and meeting the requirements of sustainable development. The vigorous development of environmentally friendly biodegradable polymer materials has attracted widespread attention from all over the world. China is no exception. In this regard, the state has continuously increased investment in scientific research in this area, and it has been included in major research plans such as national support projects.
因此，用蛋壳粉作为填料填充聚乳酸复合材料，即可降低废弃蛋壳带来的环境污染，提高其经济效益，又可降低聚乳酸复合材料的生产成本，使其性价比更接近于传统塑料，拓宽其应用范围。Therefore, using eggshell powder as a filler to fill polylactic acid composite materials can reduce the environmental pollution caused by discarded eggshells, improve its economic benefits, and reduce the production cost of polylactic acid composite materials, making its cost performance closer to that of traditional plastics. , broaden its scope of application.
发明内容Contents of the invention
本发明的目的在于开发一种蛋壳粉填充聚乳酸复合材料，提供一种外表美观、力学性能好、物美价廉的聚乳酸复合材料制备技术。The purpose of the present invention is to develop a polylactic acid composite material filled with eggshell powder, and to provide a polylactic acid composite material preparation technology with beautiful appearance, good mechanical properties, high quality and low price.
为实现以上目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种蛋壳粉填充聚乳酸复合材料，其特征在于该复合材料的组成以质量份计为：A polylactic acid composite material filled with eggshell powder is characterized in that the composition of the composite material is calculated in parts by mass:
在上述蛋壳粉填充聚乳酸复合材料中，所述的蛋壳粉按下述方法制备：In the polylactic acid composite material filled with eggshell powder, the eggshell powder is prepared as follows:
1.蛋壳的预处理：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；1. Pretreatment of eggshells: wash the eggshells with water, remove the cuticle, dry, and crush;
2.将碾碎过的蛋壳小块用粉碎机粉碎或用球磨机粗磨，100～120℃下干燥8～10h，过筛至100、200、400目。2. Crush the crushed eggshell pieces with a pulverizer or roughly grind them with a ball mill, dry at 100-120°C for 8-10 hours, and sieve to 100, 200, 400 mesh.
在上述的蛋壳粉填充聚乳酸复合材料中，所述的润滑剂为硬酯酰胺、油酸酰胺、芥酸酰胺、乙撑基双硬酯酰胺、亚烷基双硬酯酰胺、硬脂酸锌或硬脂酸钙中的一种。In the above-mentioned polylactic acid composite material filled with eggshell powder, the lubricant is stearamide, oleic acid amide, erucamide, ethylene bis stearamide, alkylene bis stearamide, stearic acid One of zinc or calcium stearate.
在上述的蛋壳填充聚乳酸复合材料中，所述的热稳定剂为顺丁烯二酸酐或环氧大豆油。In the above eggshell-filled polylactic acid composite material, the heat stabilizer is maleic anhydride or epoxidized soybean oil.
在上述的蛋壳粉填充聚乳酸复合材料中，所述的抗氧剂为四季戊四醇酯、丙酸十八醇酯或1，1，3-三(2-甲基-4-羟基-5叔丁基苯基)丁烷中的一种。In the above-mentioned polylactic acid composite material filled with eggshell powder, the antioxidant is tetraerythritol ester, stearyl propionate or 1,1,3-tris(2-methyl-4-hydroxyl-5 tertiary One of butylphenyl) butanes.
本发明还提供上述聚乳酸复合材料的制备方法，该方法包括以下步骤：The present invention also provides the preparation method of above-mentioned polylactic acid composite material, and this method comprises the following steps:
a)混合：按质量份计，将聚乳酸68～98份，蛋壳粉1～30份，润滑剂0.5～2.0份，热稳定剂0.1～1.0份，抗氧剂0.5～2.0份，其中聚乳酸的粘均分子量为10～30万；进行混合，混合后放入高速搅拌机中搅拌均匀；a) Mixing: In parts by mass, 68-98 parts of polylactic acid, 1-30 parts of eggshell powder, 0.5-2.0 parts of lubricant, 0.1-1.0 parts of heat stabilizer, 0.5-2.0 parts of antioxidant, among which poly The viscosity-average molecular weight of lactic acid is 100,000 to 300,000; after mixing, put it into a high-speed mixer and stir evenly;
b)挤出造粒：将上述搅拌均匀的成分放入双螺杆挤出机中挤出造粒；b) extrusion granulation: put the above-mentioned uniformly stirred ingredients into a twin-screw extruder to extrude granulation;
c)注塑成型：将上述复合材料粒子注塑成弯曲、冲击、拉伸样条，待测。c) Injection molding: the above-mentioned composite material particles are injection-molded into bending, impact, and tensile splines to be tested.
本发明的优点是：The advantages of the present invention are:
(1)由于本发明的复合材料采用聚乳酸为主要原料，与天然废弃物蛋壳粉进行熔融共混，复合材料为完全可生物降解材料；具有优异的力学性能，其中拉伸强度可以高达40～60MPa。(1) Since the composite material of the present invention adopts polylactic acid as the main raw material, it is melt-blended with natural waste eggshell powder, and the composite material is a completely biodegradable material; it has excellent mechanical properties, and wherein the tensile strength can be as high as 40 ~60MPa.
(2)本发明采用的蛋壳粉是一种天然废弃物，若不利用会造成环境污染，因此将蛋壳收集起来，进行综合利用，既可增加经济效益，又可避免对生态环境的污染。(2) The eggshell powder adopted in the present invention is a kind of natural waste, if not utilized, it will cause environmental pollution, so eggshells are collected and comprehensively utilized, which can increase economic benefits and avoid pollution to the ecological environment .
(3)本发明采用的蛋壳粉价格低，且在复合材料中的含量可高达30wt％而不影响聚乳酸复合材料的力学性能，大大降低了制品的成本。(3) The price of eggshell powder adopted in the present invention is low, and the content in the composite material can be as high as 30wt% without affecting the mechanical properties of the polylactic acid composite material, which greatly reduces the cost of the product.
(4)本发明蛋壳粉填充聚乳酸基复合材料的制备技术，工艺流程简单，加工性能强，成本低可实现大规模工业化生产。(4) The preparation technology of the polylactic acid-based composite material filled with eggshell powder of the present invention has simple process flow, strong processability, low cost and large-scale industrial production.
具体实施方式Detailed ways
下面结合实施例对本发明进行详细描述。The present invention will be described in detail below in conjunction with the examples.
本发明中提到的聚乳酸粘均分子量为10～30万。The polylactic acid mentioned in the present invention has a viscosity-average molecular weight of 100,000 to 300,000.
本发明中提到的填料为蛋壳粉，其主要成分为：碳酸钙94.54％、蛋白质1.15％、碳酸镁和磷酸钙4.36％，粒径范围为100～400目。The filler mentioned in the present invention is eggshell powder, and its main components are: 94.54% calcium carbonate, 1.15% protein, 4.36% magnesium carbonate and calcium phosphate, and the particle size range is 100-400 mesh.
在聚乳酸的稳定体系中，主要防止其热降解，因此常常加入热稳定剂，如顺丁烯二酸酐或环氧大豆油。In the stabilization system of polylactic acid, it is mainly to prevent its thermal degradation, so a thermal stabilizer, such as maleic anhydride or epoxidized soybean oil, is often added.
为改善聚乳酸树脂在成型加工时的流动性和脱模性，通常需要加入润滑剂，常见的如硬脂酸盐、脂肪酰胺等，其用量一般为0.05～2.0％，最宜用量为0.2～0.4％。同时这类物质还起到改善蛋壳粉分散性的作用。In order to improve the fluidity and release properties of polylactic acid resin during molding and processing, it is usually necessary to add lubricants, such as stearate, fatty acid amide, etc., the dosage is generally 0.05-2.0%, and the optimum dosage is 0.2- 0.4%. Simultaneously, these substances also play a role in improving the dispersibility of eggshell powder.
聚乳酸在加工、储存、使用过程中会受到氧和臭氧的作用而发生反应，会引起分子链降解或交联，从而使制品性能下降，因而常常需要加入抗氧剂，如四季戊四醇酯、丙酸十八醇酯或1，1，3-三(2-甲基-4-羟基-5叔丁基苯基)丁烷。Polylactic acid will react under the action of oxygen and ozone during processing, storage and use, which will cause molecular chain degradation or crosslinking, thereby reducing the performance of the product. Therefore, it is often necessary to add antioxidants, such as tetraerythritol ester, acrylic acid stearyl acid or 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane.
实施例1Example 1
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用粉碎机粉碎，120℃下干燥8h，过筛至100目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; crush the crushed small pieces with a pulverizer, dry at 120°C for 8 hours, sieve to 100 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量19.5W)78份、蛋壳粉(100目)20份、润滑剂乙撑双硬酸酯酰胺1.3份、热稳定剂顺丁烯二酸酐0.2份、抗氧剂四季戊四醇酯0.5份在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In parts by mass, 78 parts of vacuum-dried polylactic acid (weight-average molecular weight 19.5W), 20 parts of eggshell powder (100 mesh), 1.3 parts of lubricant ethylene bisstearate amide, and heat stabilizer cisbutene di Mix 0.2 parts of acid anhydride and 0.5 parts of tetraerythritol ester of antioxidant at room temperature in a high-speed mixer, extrude and granulate in a twin-screw extruder at an extrusion temperature of 160-185°C, and then inject the composite material particles into impact , Bending and stretching splines to be tested, and their mechanical properties are shown in Table 1.
实施例2Example 2
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用球磨机粗磨，120℃下干燥8h，过筛至200目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; grind the crushed pieces with a ball mill, dry at 120°C for 8 hours, sieve to 200 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量12.87W)78份、蛋壳粉(200目)20份、润滑剂乙撑双硬酸酯酰胺1.3份、热稳定剂环氧大豆油0.2份、抗氧剂四季戊四醇酯0.5份、在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In parts by mass, 78 parts of vacuum-dried polylactic acid (weight average molecular weight 12.87W), 20 parts of eggshell powder (200 mesh), 1.3 parts of lubricant ethylene bis stearate amide, heat stabilizer epoxy soybean oil 0.2 parts, 0.5 parts of antioxidant tetraerythritol ester, mixed in a high-speed mixer at room temperature, extruded and granulated in a twin-screw extruder, the extrusion temperature is 160-185 ° C, and then the composite material particles are injection molded into impact , Bending and stretching splines to be tested, and their mechanical properties are shown in Table 1.
实施例3Example 3
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用粉碎机粉碎，120℃下干燥8h，过筛至200目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; crush the crushed small pieces with a pulverizer, dry at 120°C for 8 hours, sieve to 200 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量19.5W)68份、蛋壳粉(200目)30份、润滑剂乙撑双硬酸酯酰胺1.3份、热稳定剂顺丁烯二酸酐0.2份、抗氧剂丙酸十八醇酯0.5份、在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In terms of parts by mass, 68 parts of vacuum-dried polylactic acid (weight average molecular weight 19.5W), 30 parts of eggshell powder (200 mesh), 1.3 parts of lubricant ethylene bis stearate amide, heat stabilizer maleic diethyl 0.2 parts of acid anhydride, 0.5 parts of stearyl propionate antioxidant, mixed at room temperature in a high-speed mixer, extruded and granulated in a twin-screw extruder, the extrusion temperature is 160-185 ° C, and then the composite material The particles were injection molded into impact, bending and tensile splines to be tested, and their mechanical properties are shown in Table 1.
实施例4Example 4
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用粉碎机粉碎，120℃下干燥8h，过筛至400目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; crush the crushed small pieces with a pulverizer, dry at 120°C for 8 hours, sieve to 400 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量19.5W)78份、蛋壳粉(400目)20份、润滑剂乙撑双硬酸酯酰胺1.3份、热稳定剂顺丁烯二酸酐0.2份、抗氧剂丙酸十八醇酯0.5份、在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In terms of parts by mass, 78 parts of vacuum-dried polylactic acid (weight average molecular weight 19.5W), 20 parts of eggshell powder (400 mesh), 1.3 parts of lubricant ethylene bis stearate amide, and heat stabilizer maleic acid 0.2 parts of acid anhydride, 0.5 parts of stearyl propionate antioxidant, mixed at room temperature in a high-speed mixer, extruded and granulated in a twin-screw extruder, the extrusion temperature is 160-185 ° C, and then the composite material The particles were injection molded into impact, bending and tensile splines to be tested, and their mechanical properties are shown in Table 1.
实施例5Example 5
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用粉碎机粉碎，120℃下干燥8h，过筛至400目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; crush the crushed small pieces with a pulverizer, dry at 120°C for 8 hours, sieve to 400 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量12.87W)68份、蛋壳粉(400目)30份、润滑剂芥酸酰胺1.3份、热稳定剂顺丁烯二酸酐0.2份、抗氧剂四季戊四醇酯0.5份、在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In parts by mass, 68 parts of vacuum-dried polylactic acid (weight average molecular weight 12.87W), 30 parts of eggshell powder (400 mesh), 1.3 parts of lubricant erucamide, 0.2 part of heat stabilizer maleic anhydride, Antioxidant tetraerythritol ester 0.5 parts, mixed in a high mixer at room temperature, extruded and granulated in a twin-screw extruder, the extrusion temperature is 160-185 ℃, and then the composite material particles are injection molded into impact, bending, Tensile splines are to be tested, and their mechanical properties are shown in Table 1.
实施例6Example 6
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用球磨机粗磨，120℃下干燥8h，过筛至100目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; grind the crushed pieces with a ball mill, dry at 120°C for 8 hours, sieve to 100 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量12.87W)68份、蛋壳粉(100目)30份、润滑剂乙撑双硬酸酯酰胺1.3份、热稳定剂顺丁烯二酸酐0.2份、抗氧剂四季戊四醇酯0.5份、在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In terms of parts by mass, 68 parts of vacuum-dried polylactic acid (weight-average molecular weight 12.87W), 30 parts of eggshell powder (100 mesh), 1.3 parts of lubricant ethylene bisstearate amide, heat stabilizer maleadiene di 0.2 part of acid anhydride, 0.5 part of tetraerythritol ester of antioxidant, mixed in a high-speed mixer at room temperature, extruded and granulated in a twin-screw extruder, the extrusion temperature is 160-185 ° C, and then the composite material particles are injection molded into Impact, bending and tensile splines are to be tested, and their mechanical properties are shown in Table 1.
实施例7Example 7
蛋壳粉的制备工艺：将蛋壳用水清洗干净，去除表面角质层，干燥，碾碎；将碾碎过的小块用球磨机粗磨，120℃下干燥8h，过筛至200目，备用。The preparation process of eggshell powder: wash the eggshell with water, remove the surface cuticle, dry, and crush; grind the crushed pieces with a ball mill, dry at 120°C for 8 hours, sieve to 200 mesh, and set aside.
按质量份计，将真空干燥的聚乳酸(重均分子量12.87W)88份、蛋壳粉(200目)10份、润滑剂芥酸酰胺1.3份、热稳定剂环氧大豆油0.2份、抗氧剂四季戊四醇酯0.5份、在高搅机中常温混匀，在双螺杆挤出机中挤出造粒，挤出温度为160-185℃，然后将复合材料粒子注塑成冲击、弯曲、拉伸样条，待测，其力学性能见表1。In parts by mass, 88 parts of vacuum-dried polylactic acid (weight average molecular weight 12.87W), 10 parts of eggshell powder (200 mesh), 1.3 parts of lubricant erucamide, 0.2 part of heat stabilizer epoxy soybean oil, anti- Oxygen agent tetraerythritol ester 0.5 part, mixed in a high-speed mixer at room temperature, extruded and granulated in a twin-screw extruder, the extrusion temperature is 160-185 ° C, and then the composite material particles are injection molded into impact, bending, tensile Stretch splines to be tested, and their mechanical properties are shown in Table 1.
表1实施例1～7所制备的聚乳酸组合物的性能The performance of the polylactic acid composition that table 1 embodiment 1～7 prepares
从表中可以看出，该发明所制备的蛋壳粉/贝壳粉填充聚乳酸基复合材料，具有良好的力学性能，符合一般塑料的使用要求，尤其能降低生产成本，变废为宝，减少环境污染，提高生产效率。上述对实例的描述是为了便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域的技术人员可以容易对这些实施实例做出各种修改，并把在此说明的一般性原理应用在其它应用实例中而不必经过创造性的劳动。因此，本发明不限于这里的实施实例，本领域技术人员根据本发明的揭示，对本发明做出的改进和修改都应该在本发明的保护范围之内。It can be seen from the table that the polylactic acid-based composite material filled with eggshell powder/shell powder prepared by the invention has good mechanical properties and meets the requirements for the use of general plastics, especially can reduce production costs, turn waste into treasure, reduce Environmental pollution, improve production efficiency. The above description of the examples is to facilitate those of ordinary skill in the art to understand and apply the present invention. Those skilled in the art can easily make various modifications to these implementation examples, and apply the general principles described here to other application examples without creative efforts. Therefore, the present invention is not limited to the implementation examples here, and the improvements and modifications made by those skilled in the art according to the disclosure of the present invention should be within the protection scope of the present invention.
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| US8829097B2 (en) | 2012-02-17 | 2014-09-09 | Andersen Corporation | PLA-containing material |
| EP2774655A1 (en) | 2013-03-05 | 2014-09-10 | JAO beheer BV | Composition comprising chicken eggshell particles, preparation and use |
| CN104559282A (en)* | 2015-01-26 | 2015-04-29 | 王文广 | Biological calcium carbonate filling master batch |
| KR101636053B1 (en)* | 2016-01-27 | 2016-07-08 | 주식회사 에코원 | Resin Composition Comprising Egg-shell Powder |
| CN106400582B (en)* | 2016-09-27 | 2018-04-10 | 珠海乐桐实业发展有限公司 | A kind of preparation method of composite filler for papermaking |
| TWI748511B (en)* | 2020-06-11 | 2021-12-01 | 力陞綠色科技有限公司 | Disposable egg shell environmental protection material and manufacturing method |
| CN112848422A (en)* | 2020-12-30 | 2021-05-28 | 江苏光辉包装材料有限公司 | Preparation method of biological heat-reducing shrink label film |
| CZ35169U1 (en)* | 2021-04-20 | 2021-06-15 | Technická univerzita v Liberci | Biopolymer composite material based on polylactic acid |
| CN114854178B (en)* | 2022-05-25 | 2023-05-02 | 宁波勤邦新材料科技有限公司 | Optical adhesive release film base film and manufacturing method thereof |
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